Use of carbon-13 substituent chemical shifts to scale non-hydrogen-bonding dipolar interactions of protonic solvents

B. Chawla, S. K. Pollack, C. B. Lebrilla, M. J. Kamlet, R. W. Taft

Research output: Contribution to journalArticle

32 Citations (Scopus)

Abstract

The aromatic 13C NMR shifts induced by protonic solvents in very dilute solutions of benzotrifluoride and phenylsulfur pentafluoride provide a novel means of scaling the dipolar character of these bulk solvents with little or no effects from solute-solvent hydrogen bonding. That is, these shifts have been utilized to define π solvatochromic parameters for 17 (OH, NH, and CH) protonic solvents. These results agree with previously obtained values for the strongly self-associated alcohols. However, for other more weakly self-associated solvents, evidence is presented that the method gives more reliable π values and provides the means for scaling hydrogen-bond donor abilities (α values) of relatively strong protonic solvents. The widely varying sensitivities (s) to solvent dipolarity of the para-carbon atom substituent chemical shifts for monosubstituted benzenes are determined by both the substituent-induced polarization of the benzene π electrons and by the substituent π-electron delocalization to or from the ring. This is shown by a unique DSP correlation of the s values.

Original languageEnglish (US)
Pages (from-to)6924-6930
Number of pages7
JournalJournal of the American Chemical Society
Volume103
Issue number23
StatePublished - 1981
Externally publishedYes

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Chemical shift
Carbon
Benzene
Hydrogen bonds
Electrons
Hydrogen Bonding
Hydrogen
Alcohols
Nuclear magnetic resonance
Polarization
Atoms

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Chawla, B., Pollack, S. K., Lebrilla, C. B., Kamlet, M. J., & Taft, R. W. (1981). Use of carbon-13 substituent chemical shifts to scale non-hydrogen-bonding dipolar interactions of protonic solvents. Journal of the American Chemical Society, 103(23), 6924-6930.

Use of carbon-13 substituent chemical shifts to scale non-hydrogen-bonding dipolar interactions of protonic solvents. / Chawla, B.; Pollack, S. K.; Lebrilla, C. B.; Kamlet, M. J.; Taft, R. W.

In: Journal of the American Chemical Society, Vol. 103, No. 23, 1981, p. 6924-6930.

Research output: Contribution to journalArticle

Chawla, B, Pollack, SK, Lebrilla, CB, Kamlet, MJ & Taft, RW 1981, 'Use of carbon-13 substituent chemical shifts to scale non-hydrogen-bonding dipolar interactions of protonic solvents', Journal of the American Chemical Society, vol. 103, no. 23, pp. 6924-6930.
Chawla, B. ; Pollack, S. K. ; Lebrilla, C. B. ; Kamlet, M. J. ; Taft, R. W. / Use of carbon-13 substituent chemical shifts to scale non-hydrogen-bonding dipolar interactions of protonic solvents. In: Journal of the American Chemical Society. 1981 ; Vol. 103, No. 23. pp. 6924-6930.
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